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Патент USA US3045066

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July 17, 1962
A.scHR1EsHE1M l-:T AL
3,045,056
SUPPORTED CATALYST PARAFF'IN ALKYLATION PROCESS
Filed Nov. :5, 195e
LIGHTER
HYDROCABN
FE D
AIon Schriesheim
George R. Gilberî
By ë
Inventors
y M AHorney
kUnited kStates Patent
l
i
2
PROCESS
Alan Schriesheim, Fords, and George R. Gilbert, Eliza
beth, NJ., assignors to Esso Research and Engineering
Company, a corporation of Delaware
3,645,056 .
Patented July 17, 1962
The nature and objects of this invention and the manner
in which the invention can be practiced will be more
readily understood when reference is made to the accom
.
„
s 04 5,056
SUPPÜRTED CATALYÉT PARAFFIN ALKYLATIUN .
_
Ce
5
panying drawing yin which the single FIGURE is a sche
matic flow plan of one process for practicing the invention.
The process will be described with particular reference-
to the use of isobutane as the lighter component. Refer
Filed Nov. 3, 1958, Ser. No. 771,319
6 Claims. (Cl. 260-683.53)
ring to the drawing in detail, a suitable butane feed stream
containing at least initially a major proportion of iso
The present invention relates to the alkylation of paraf 10 butane is obtained by means of line 11 from a suitable
ñn hydrocarbons with other paraffin hydrocarbons. It
source. A portion of the stream is conducted Via line 11a
involves the preparation of branched> chain parañin hydro
through an aluminum bromide pick-up vessel 12 to dis
cal-bons boiling in the motor fuel range by the reaction
solve aluminum bromide in a portion of the streamthat
of a butane or a pentane, preferably isobutane, with other
is conducted to the reaction Zone. The remaindergof the
paraffin hydrocarbons of 6 or more carbon atoms in a ll5 feed stream is combined -with the effluent leaving the
process involving simultaneous cracking, isomerization
pick-up vessel via line 13 and is conducted Vinto a reaction
and alkylation reactions. More specifically, the inven
tion concerns a process wherein a butane or a pentane is
reacted with a paraffin hydrocarbon of from `6 to 18
zone 15.
The latter zone contains one or more beds of
calcined bauxite saturated with aluminum bromide.
A stream of a higher parañ‘in hydrocarbon, as for
carbon atoms in the presence of aluminum bromide and a ' 20 example heptane, octane, dodecane or cetane, or of mix
promoter support under conditions that favor the pro
duction of high yields of branched chain paraffin hydro
carbons of 5 to 7 carbon atoms.
A major problem in petroleum refining is to secure from
tures containing the higher parafiins, is conducted into the
reaction zone by means of line 16. Preferably the stream
enters the reaction Zone at a plurality of spaced points,
16a, 1619, etc., so as to insure as high a ratio as possible
the hydrocarbon sources ‘available a sufficient quantity 25 of isobutane to vhigher paraiïin at any particular point in
of high octane rating hydrocarbons boiling in the motor
fuel range to satisfy the demands of modern high com
pression engines.A Processes for producing the high octane
components must not be too costly and must have a
the reaction zone.
,
The reaction product leaves the reaction zone through
line 18 and is conducted into an initial separation zone
20 wherein light materials, including unreacted isobutane
reasonable degree of versatility. Hertofore a number of 30 and normal butane, are removed overhead andrecycled
processes have been available which use C3 and C4 .petro
to the reaction zone by means of line 21. Hydrogen bro
leum fractions from various sources such as natural gaso
line plants, distillate recovery plants and various petroleum
mide, if present, will also be recycled via line _211. The
heavier material, `including C5 hydrocarbons and higher,
reñnery streams, and which convert those fractions to
is conducted by means of line 22 into a product sepa
motor fuel components by polymerization reactions or 35 ration zone 24 wherein C5 to C7 hydrocarbons arel re-V i
by alkylation reactions. For example, isobutane can be
moved overhead by means of line 2S while heavier mate
reacted with butylene in the presence of sulfuric acid to
rial comprising C8 hydrocarbons and higher as well as any
give a branched-chain 8-carbon-atom alkylate. Also
aluminum bromide that has been removed from the re
butylene can be polymerized to a C8 unsaturated hydro
action zone is recycled to` the reaction zone by means of
carbon which upon hydrogenation will give isooctane. 40 line 26. >‘If desired, conditions can be adjusted in sepa
These processes have some disadvantages in that they
ration zone 24 to include normal heptane in the heavier
require a number of separate operations and in that they
material recycled through line 26, while including the C7
necessitate the use of olelins, which are usually in rela
branched chain isomers in overhead line 25.
.
tively limited supply.
'
In place of isobutane the feed in line 11 may comprise
It has now been found that, by the use of a promoted 45 normal butane, in which case no higher hydrocarbon feed
aluminum bromide catalyst, butanes and/ or pentanes can
stock will be sent initially to the reaction zone |but the
, be reacted directly with higher paraflin hydrocarbons to
butane will be recycled through' line 18, zone 20 and line
give good yields of C5 to C7 branched chain hydrocarbons
of high octane rating, provided certain speciiic conditions
21 until a considerable amount of the butane has been
with a large excess of a butane or a pentane, >preferably
distribution of the products may be obtained.
isomerized to isobutane. The process may then continue
are employed. It has previously been proposed to con 50 in the manner already described, the recycle isobutane
duct reactions of this type but yields have been low, re
being sufficient to make the desired reaction proceed while
action rates have been uneconomic and satisfactory prod~
the fresh butane feed becomes isomerized to isobutane in
uct distribution has not been obtained.
the reactor.
~
In accordance with the present invention, a` parañin
A number of factors in the process of the present in
hydrocarbon of from 6 to 18 carbon atoms is reacted
vention are critical to its operation in order that proper
For ex- '
isobutane, employing as a catalyst AlBr5 supported on
ample, at temperatures above about 140° F. considerable
or associated with calcined bauxite, at temperatures in
cracking occurs and the principal products are propane
the range of from about 30° to about -140" F. and at
and lighter materials. Also it has been established that
pressures suñ'icient to keep the reacting hydrocarbons in 60 aluminum bromide alone or even in the presence of con
the liquid phase. The products of the reaction are satu
ventional hydrogen halide promoters such as hydrogen
rated branched chain paraflin hydrocarbons predominantly
bromide, in the absence of the support, is very much less
in the C5 to C7 range. The preferred temperature range
active
than the catalyst system of the present invention.
is from about 50° to about 120° F.
Furthermore in order for the reaction to proceed satis
3,045,053
3
factorily it is necessary that sufficient aluminum bromide
be present not only to saturate the support under the reac~
tion conditions employed but also to leave at least a small
amount dissolved in the reacting hydrocarbons.
A mixed catalyst in which a portion of the aluminum
bromide is replaced with aluminum chloride may be
used provided that at least some aluminum bromide is
present in the reacting hydrocarbons over and above that
which is adsorbed on the support.
4
A calcined bauxite that may be employed as the cata
lyst promoter in the present invention can be obtained
commercially under the trade name “Porocel” Before
the bauxite is used it should be dehydrated. A suitable
pretreatment for this purpose involves heating for from
about 3 to 5 hours at 1100" to 1200" F.
At the start of the process the calcined bauxite may
be saturated with aluminum bromide and then placed in
the reaction zone, or, alternatively, the bauxite alone may
used as an auxiliary promoter in addition to the calcined
bauxite. A range of from about 0.1 to 8% or more
be placed in the reaction zone and then saturated with
aluminum bromide carried in with a portion of the feed.
Another method of preparation is to mix the aluminum
halide with the support and to heat the mixture to effect
of HBr by weight based on total feed may be used, while
from about 0.3 to about 5% is preferred. When hy
drogen bromide is employed it is introduced into the reac
mass and passing through it a gas such as carbon dioxide,
Although the reaction may proceed in the absence of
hydrogen bromide promoter it is preferred that it be
tion zone by means of line 17 and will be recycled to the
reaction zone along with unreacted butanes by means of
line 21.
Although the process as described in conjunction with
the drawing contemplates downtlow of the stream through
the catalyst bed, which is preferred, upñow can also be
used.
Also in place of a tixed bed process, a moving bed
of catalyst could be used. Alternatively, a slurry type of
operation could be employed 4wherein a suspension of
catalyst is maintained in the reacting hydrocarbons, the
slurry being stirred in the reactor with suitable mechani
cal stirring means or recirculated through the reactor by
pumping means. Where slurry operation is used, the
impregnation. If desired, loosely held aluminum halide
may be removed from the catalyst mass by heating the
methane, hydrogen or nitrogen.
Alternatively the support may be impregnated by dis
solving the aluminum halide in a suitable solvent such
as ethylene dichloride or dioxane, for example, and the
porous carrier impregnated with this solution, followed
by heating to remove the solvent and loosely held alumi
num halide. Still another alternative is to employ a pow
dered support or promoter, mix the aluminum halide with
it, and compress the mixture into pellets.
The following examples serve to illustrate the prac
tice of the present invention.
EXAMPLE 1
Comparative tests were made in which in each in
slurry is removed from the reactor at the end of the reac 30 stance a mixture of 160 cc. of isobutane and 40 cc. of
tion period, in the case of batch operation, or as a frac
a normal heptane feed (containing 95% n-C», and 5% of
tion of the circulating stream in the case of continuous
methylcyclohexane) was stirred for 3 hours at 72° F.
operation, and sent to suitable separation equipment to
separate the catalyst from the hydrocarbons. The sepa
ration equipment may comprise a simple settling tank, a
centrifuge, or a filter, for example, or suitable combina
with one of the catalyst systems identified in Table I.
At the end of each run the yield of products was deter
mined, the results also being presented in Table I.
tions of such means.
TABLE I
It is preferred that the minimum mol ratio of isobutane
and/or isopentane to higher parañìn be about 3 to 1 but
Test 1
should preferably be no higher than about l2 to 1. If 40
sufficient iso-C4 is not present in the reaction zone to
Catalyst, grams:
effect alkylation of the materials obtained when a higher
A1Bri .......................... _23.0
parañìn or other higher product of the reaction is cracked
by the catalyst, catalyst sludging will result. The feed
stock must be essentially free of aromatic hydrocarbons
and not more than about 0.02% of such material should
0.4
0.3
be tolerated in the feed stock up to about 20 volume per
cent. With increased naphthene content the reaction
severity must be increased somewhat as compared to a
reaction in the absence of naphthenes. This may be ac
complished by raising the temperature and/or lowering
Feed rates may vary from about 0.3 to about 2 v./hr./v.
Test 3
Test 4
23.6
23.0
23.5
.
47.2
17.0
Analysis of 05+ Product, Weight
percent:
be present. .An added advantage of the catalysts of the
present invention is that naphthene hydrocarbons may
the feed rate, for example.
Test 2
Total C1 ..................... _.
0.5
3.3
22.7
2.9
33.5
5.0
0.7
4.1
25.0
39.4
0.5
-0
0.3
0
15.1
0.6
23.5
1.1
0.5
0.3
15.7
24.5
40. 2
52.5
4s. 3
47.3
56. 5
2.2
32. 5
3.5
93.8
05.0
53.7
35.0
(liquid volume of total feed per hour per volume
of total catalyst plus support) the higher feed rates be
It will be seen from the results of these comparative
ing preferred when little or no naphthenes are present.
tests that aluminum bromide alone, or even in the pres
To remove aromatics from the feed stock conventional
ence of hydrogen bromide, was not effective in produc
techniques may be employed such as solvent extraction,
ing the desired reaction. In both of these instances the
hydrogenation, acid treating and the like, as well as
major proportion of the reaction products comprised C7
treatment with selective adsorbents such as molecular
hydrocarbons. The aluminum bromide merely served
sieve zeolites. It is not necessary that the higher hydro
as an isomeiization catalyst. On the other hand, in the
carbons used be individual hydrocarbons such as heptane
tests in which aluminum bromide and Porocel either
or octane or cetane, for example, but mixtures may be 65 alone or in conjunction with hydrogen bromide were em
used, such as a petroleum fraction containing parañ‘inic
ployed as the catalyst, considerable yields of C5 and C,
hydrocarbons in the range of 6 to 18 carbon atoms. A1
isomers were obtained.
though, as stated, hexane is one of the higher hydro
EXAMPLE 2
carbons that may be used, it is preferred to employ
heptane or higher. Essentially the same product dis 70 In a manner similar to that employed in Example 1
comparative tests were made with a number of other
tribution is obtained with hexane as with heptane but
supports or promoters in addition to Porocel. These in
the reaction rate is lower by a factor of about 3. Other
cluded Fe203 and FeCl3 which are known to have high
sources of the higher paraffin hydrocarbons for the reac
tion include light virgin naphthas, and parafiin rañinates
from the extraction of hydroforrned petroleum fractions.
activity for promoting isomerization reactions. The re
sults obtained are shown in Table II.
á,04'5,056
Tests
5
l6
TABLE II
EXAMPLE 5~
In another series of tests conducted in the same man
Tes”
Testö
23.6
23.6
Test?
Tests
ner as described in Example 1, the effect of thefratio
of isobutane to heptane on the yield of C5 to C7 branched
'
Cßtïïâtlïs,
grams___--
_
23.6 '
ÈÍ‘ÃIÄÈÍQL" Porocel
promoter.-
Fem’
47.2
47.2
F901’
t
5 chain hydrocarbons was determined.
23.6
23.6
m
11.8
A120’
47.2 .
39 grams of aluminum chloride and 119 grams of ‘Poro~
47.2
ce1.
Analysis of 05+
The reaction temperature was 100° F., the pressure
was 300 p.s.i.g. and each reaction consumed 2 hours, the
ärgiêtâìt,
10 normal heptane being added gradually during the entire
percent;
ìlsfèCß ----- --
react1on period. The results obtained are given in Table
IV and show that the yield of C5+ hydrocarbons in
(lig
ß ------ --
-
-
'
'
'
25.6
1.5
1.8
2_1
L8
ti
3'8
t1
3:3
93.2
1_9
62.9
0_8
46.1
1.1 '
65.0
0.4
’
' 133%
isœoy
Total
.....
can."
._
The catalyst ín
these tests consisted of 20 grams of aluminum bromide,
56.5
15.7>
creased as the ratio of isobutane to heptane was increased
n-C1 ______ _-
2.2
3.4
34.5
50.7
22.8
Tota1C7--.
58.7
96.6
97.4
96.8
97.8
over a mol ratio range of about 3 to 1 to about 10 to 1.
l5
-
. TABLE 1V
EÜECÍ_ 0f ISObLlÍal1e~ÍO Hepfaì’le RIZÍÍO 0n
20
Feed Composition:
Grams, Isobutane ________________ -_
„ Grams, n-Heptane ................ -_
285
170
285
85
285
33
Ylelds, Wt. percent on Heptane Feed:
C; and less _______________________ __
1 Allos-90%, rezos-10%.
6
05+ ............................
10
122
153
It will be seen that neither alumina, ferrie chloride nor
36
170
~
FeZOs was effective in promoting the desired reaction.
The alumina used in the above tests Was found to be of
sgi;
4,2%
3?:
the eta formi In each case the principal product com
prised 1C», hydrocarbons although some isomerization of
40'2
48‘9
44
the latter had occurred.
21.1
24.2
` 12.
.
1.4
1.4
0.
In a similar manner, another series of tests were `run
EXAMPIE 3
Y
30
l
22'5
25'6
13'
30.
at temperatures of 72 to 75° F. with the same feed com-
23.9
22.1
position and the same feed-to-catalyst support ratio as in
9'1
L1'
12'
Example 1 (200 cc. total feed to 47 fgrams of Porocel)
33.0
« 23.2
42.
using various metal halides other than laluminum bro- 35
mide, in the ratio of 24 grams of halide to 47 grams of
Porocel. The metal halides used were aluminum chlo~
EXAMPLE 6
.
Employing the same catalyst mixture as was used in
Example 5, »tests were made in which normal octane, nor
The concentration of aluminum fluoride 40 mal cetane and normal octadecane were lsubstituted for
ride, aluminum iodide, aluminum lluoride, bismuth tri
chloride, ferrie chloride, tin tetrachloride and titanium
tetrachloride.
on Porocel was slightly lower than with the other metal
halides. None of these metal halides Was found to have
any apparent activity for the desired reaction under the
the normal heptane.
runs. The reaction pressure in each instance was 300
p.s.i.g. :and 2-hour reaction times were used. It lWill be
conditions employed.
'
The reaction temperature wasl
120° F. inthe case of yoctadecane and 100° F. in the other
seen fronrthe data in Table V that the product distribu
tion was essentially the same regardless of the higher
EXAMPLE L1
In another group of tests the effect of naphthenes »on
parat-lin used.
.
the reaction was determined. Using the catalyst system
'
TABLE V
of Test 3 of Example 1 and the same reacting hydrocar
Comparison of Reactions With Hydrocarbons of 7 to 18
bon mixture as in that test, but varying the percentage of
naphthenes, it was found that as the concentration of 50
Carbon Atoms
methylcyclohexane in the normal heptane feed was in«
creased from 1 volume percent to V20 volume percent the
relative rate of conversion of heptane to C5 and C6
branched chain hydrocarbons was reduced by a factor of
3. It was also found that the inhibiting effect of naph 55
Feed Composition
Heptane Octane Cetane Octadecane
'
342
Grams, Isobutane ____________ ._
Grams, Heavier Parati‘in.>____ ._
05+ _____________ _-
_
temperature from 100° F. to 115° F. when 8% of methyl
Analysis of 05+ Product,
cyclohexane was present brought about a doubling of the
Weight Percent:
reaction rate, as measured by the weight percent 0f C7 60
iso-C5 ____________________ __
11-05 _____________________ __
hydrocarbons in the C5+ product after various reaction
times. This is shown in Table III.
Total C5 ............... _-
TABLE III
Naphthenes
v
65
Weight percent C1 in
Reaction Time, Hours
C5+Product
100° F.
115° F.
1.
2
3
95
79
63
77.4
51.5
26.6
4
51.6
28
10
9
6
23
153
155
188
190
42. 1
6. 8
48.0
8. 6
i
35. 7
6.3
42. 4
9. 2
Yields, Wt. Percent on HeavC3 and less ________ _.
by raising the temperature. Thus, raising the reaction
Effect of Temperature on Reaction Rate in Presence of
285
87. 5
70
285
47. 5
48. 4
.
y
ier Parañîn:
thenes on the reaction can be overcome to some extent
p
285
85
48. 9`
56. 6
42.0
l 51. 6
24. 2
24.2
21.1
25. 5
1. 4
1. 4
1. 3
1. 8
25.6 ì
22. 4
27.3
Total Cs _______________ --
25. 6
iso-C7 ____________________ _.
22. 1
9. 7
9. 6
7.19
n-C; _____________________ _-
1. 1
0.5
0. 5
.......... ._
Total C1 _______________ _-
23. 2
10.2
10. 1
7. 9
05+ _____________________ __
2. 3
7. 6
25. 5
13. 2
EXAMPLE 7
A catalystcomposition comprising Porocel and alumi~
num bromide in a 1 to 1 Weight ratio of A1Br3 to support
75 was tested in a continuous pilot unit consisting of a
3
7
jacketed reactor provided with a Amechanical stirrer and
with a settling chamber to permit slurry operation. Reac
tion conditions were 100° F. fand 150 p.s.i.g. pressure. A
feed mixture of normal heptane and isobutane which gave
about 70 volume percent of isobu-tane in the reactor was
passed through the reactor at a space velocity of about
0.05 volume of heptane per hour per volume of the re
actor. As the catalyst occupied about 25 percent of the
reactor volume this feed rate corresponded to about 0.2
v./hr./v. of catalyst.
Aluminurn bromide was continu- l
ously added to the reaction zone as a solution in the iso-
butane in suñicient quantity to constitute a 5 to l0 weight
percent solution based on total feed. Hydrogen bromide
was also added at the rate of 1 »to 5 weight percent based
on feed. The total liquid product from the reactor was
scrubbed with 20 percent caustic to remove aluminum
bromide and H12-r, then dried, debutanizcd and analyzed.
Continuous catalyst activity was observed -for 150 to 200
hours operation, with good yields, of the order of 135 to
145 volume percent of C54- hydrocarbons, based on the
normal heptane. A similar continuous run with cetane
as the higher paraiiin lfed, using the same reaction condi
tions, the same catalyst mixture and the same ratios of
isobutane to higher parañin, gave yields of the order of
250 to 260 volume percent of C54- hydrocarbons, based
on the cetane.
In `both runs, i'.e. with heptane and with
cetane, the ratio of >C5 to CG hydrocarbons was about 2
to 1.
Other studies of continuous operation established that
in order to maintain catalyst activity it is necessary to
have present in `the reaction zone suñicient aluminum
bromide to furnish aluminum bromide in solution in Ithe
reacting hydrocarbons over and above the quantity re
quired to satisfy the total adsorption capacity of the cal
cined bauxite. To ensure this in a continuous oper-ation ~
it is preferred that suñicient aluminum bromide be dis
tane naphtha components consisting largely of branched
chain paraiiin hydrocarbons c'f '5 to 7 carbon atoms which
comprises reacting a minor proportion of a straight chain
parafñn hydrocarbon of ‘from '6 to 18 carbon atoms with
a major proportion of a lighter hydrocarbon selected
from the group consisting of butanes and pentanes, at
temperatures no higher than about 140° F., in a reaction
zone in the presence of a catalyst comprising aluminum
bromide'and calcined bauxite, supplying to the reaction
zone sufficient aluminum bromide to furnish at least 0.05
weight percent of aluminum bromide in solution in the
reacting hydrocarbons over and above the quantity re
quired to satisfy the total adsorption capacity of the
calcined bauxite.
2. Process as defined by claim 1 wherein reacting hy
drocarbons are continuously conducted into said reaction
zone and reaction products are continuously removed
from said reaction zone and wherein suiiicient aluminum
bromide is dissolved in at least one entering stream of
reacting hydrocarbons so that at least 0.05 Weight percent
of aluminum bromide is present in the products removed
from said reaction zone.
3. Process as defined by claim l wherein from about
0.1 to about 8 percent of hydrogen bromide, based on
the reacting hydrocarbons, is present in the reaction zone.
4. Process as delined by claim l wherein Vthe mol ratio
of said lighter hydrocarbon selected from the group con
sisting of butanes and pentanes to said hydrocarbon of
from 6 to 18 carbon atoms in the reaction zone is in the
range of from about 3 to 1 to about 12 to 1.
5. Process as defined by claim l wherein naphthenic
hydrocarbons are present in said reaction zone.
6. A process for the preparation of high octane naph
tha components consisting largely of branched chain
parañin hydrocarbons of 5 to 7 carbon atoms which
comprises reacting a straight chain parañin hydrocarbon
of from 6 to 18 carbon atoms with a lighter hydrocarbon
selected from the group consisting of butanes and pen
tanes, wherein the mol ratio of said lighter hydrocarbons
aluminum bromide will be present in »the products leav
40 to said straight chain paratiin hydrocarbon is in the range
ing the reaction zone.
of from about 3:1 to about 12:1, at temperatures in the
Certain modifications of the process outlined herein~
solved in at least one of the entering streams of reacting
hydrocarbons so `that at least 0.05 weight percent of
before will occur -to those skilled in the art. Such modi
ñcations are contemplated within fthe scope of the present
invention. For example, if rthe yield of C5 hydrocarbons
is larger in proportion to the C5 hydrocarbons than is de
sired, the product may be distilled to separate a C5 cut
which may `then be used in a conventional alkylation step
with an olefin »such as ethylene, propylene or a butene,
employing -the usual alkylation catalysts such as sulfuric
acid, phosphoric acid, hydrogen ñuoride, or an aluminum 50
halide. Alternatively, the C5 cut can be sent to a second
reaction zone of »the type herein described for reaction
with higher normal parañin hydrocarbons.
It is to be understood that this invention is not to be
limited to the specific embodiments »and examples herein
described and presented but that its scope is to be deter
mined solely by the claims appended hereto.
What is claimed is:
-
l. A liquid phase process for the preparation of high oc
range of about 50 to 120° F., in a reaction zone in the
presence of a catalyst comprising aluminum bromide and
calcined bauxite, supplying to the reaction zone suñicient
aluminum bromide to furnish atleast 0.05 weight percent
of aluminum bromide in solution in the reacting hydro
carbons over and above the quantity required to satisfy
the total adsorption capacity of the calcined bauxite.
References Cited in the tile of this patent
UNITED STATES PATENTS
2,349,458
Owen et al ___________ _- May 23, 1944
2,370,144
2,401,925
Burk ________________ -_ Feb. 27, 1945
Gorin _______________ __ lune 1l, 1946
2,415,061
2,506,720
2,971,037
de Simo et al __________ __ Ian. 28, 1947
.Tones ________________ __ May 9, 1950
Gilbert et al ____________ ___ Feb. 7, 1961
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